Polyurethane elastomers cured with n, nu-dimethylolethyleneurea



United States Patent 3,021,306 POLYURETHANE ELASTOMERS CURED WITH N,N-DIMETHYLOLETHYLENEUREA Ernest Csendes, Christiana Hundred, and John Joseph Verbanc, Braudywine Hundred, Del., assignors to E. I. do l en: de Nemours and Company, Wilmington, Del., a corporation of Delaware No Drawing. Filed June 30, 1958, Scr. No. 745,262

6 Claims. (Cl. 260-675) linking to take place in a reasonable length of time.

t is an object of the present invention to provide a novel process for curing polyether polyurethane polymers. A further object is to provide a process for curing such polymers with dimethylolethyleneurea in the presence of quinolinium tetrachlorczincate as a catalyst. A still further object isto provide a novel cured polyether polyurethane elastomer which has excellent physical properties. Other objects will appear hereinafter.

These and other objects of this invention are accomplished by providing a cured polyether polyurethane elastomer having a plurality of units of the formula t w Y-OGVOCYNR- I wherein --O-GO- is a. bivalent radical obtained by removing the terminal hydrogen atoms from a polyether about 5,000, said glycol being'selected from'the group consisting of polyalkyleneether glycols, polyalkyleneetherthioether glycols and polyalkylene-aryleneether glycols, and R is a bivalent organic radical which is inert to isocyanate groups. The novel cured polyether polyurethane elastomers of the present invention are obtained by curing a polyether polyurethane polymer with from about 3 to 15 percent by weight of dimcthylolethyleneurea in the presence of from about 0.1 to 1.0 percent by weight of quinolinium tetrachlorozincate. The polymer is cornpounded with the curing agent and the catalyst and then heated to a temperature of about 120 to 160 C. so as to effect a cure.

The polyether polyurethane polymers which may be cured according to the present invention may be prepared from polyether glycols, organic diisocyanates and, if desired, a chain-extending agent. The polyether glycols may .be polyalkyleneether glycols, polyalkylene-thioether glycols or polyalkylene-aryleneether glycols, which glycols have molecular weights of between about 750 and 5,000. It is to be understood that mixtures of these glycols may be used.

The polyalkyleneether glycols are compounds which may be represented by the general formula HO(GO),,H

wherein is an alkylene radical which need not necesglycol having a molecular weight of froma bou't 750 to H 3,021,305 Patented Feb. 13, 1962 sarily be the same in any particular glycol and n is an integer so that the average molecular weight of the polyalkyleneether glycol is at least about 750. These polyalkyleneether glycols may be prepared by well known methods. Representative polyalkyleneether glycols include polyethyleneether glycols, polypropyleneether glycols, polytrimethyleneether glycols, polytetrametnyleneether glycols, polyether-propyleneether glycols, etc- The polyalkyleneether-thioether glycols may be represented by the general formula set forth above for the polyalkyleneether glycols wherein part of the ether oxygens are replaced by sulfur atoms. These glycols may be prepared by well-known methods such as the catalytic dehydration of thiodiglycol and diethylene glycol.

The polyalkylene-aryleneether glycols are similar to the polyallryle'necther glycols except that some of the alkylene radicals are replaced by arylene radicals and, in addition, if desired, part of the ether oxygens may be replaced with sulfur. In general the phenylene and naphthalene radicals are preferred with or without substituents such as alkyl or alkylene groups. These glycols are described in US. Patent 2,843,568.

Any of a wide variety of organic diisocyanates may be used for reaction with the polyether glycol in preparing the polyether polyurethane polymers. Representative compounds include 2,4-tolylenediisocyanate, m-phenylenediisocyanate, 4-chloro-1,3-phenylenediisocyanate, 4,4'-diphenylenediisocyanate and 1,i-naphthalenediisocyanate. 2,4-tolylenediisocyanate is the preferred diisocyanate. in general any organic diiso'cyanate may be used which has no substituents reactive with the 'glycol other than the two isocyanate groups. Thus these diisocyanates may contain a wide variety of inert substituents such as hydrocarbon radicals, halogen radicals, nitro groups, alkoi'ry groups, etc.

In preparing the curable polyether polyurethane polymers various procedures may be employed. In onset these the polyether glycol is reacted with the organic diisocyanate in approximately stoichiometrically equivalent proportions in which case a pluralityof urethane linkages will be formed and there will be substantially no free isocyanate groups in the final polymer. The resulting product will either be a solid or a liquid polymer. The liquid polyether polyurethanes result from the use of relatively low molecular weight polyether glycols, i.e. glycols having a molecular weight ofrabout 750. The reaction of the glycol with the diisocyanate may be carried out in suitable mixing equipment at temperatures offrorn about 20 C.

to about C. I

If desired the curable polymer may be prepared by reacting the polyether glycol with a molar excess of the organic diisocyanate in which case an isocyanatc-terminated intermediate polymer will be formed. This intermediate polymcr may then be reacted with a monofunction'al compound such as alkanol in order to cap the free isocyanate groups, or, if desired, it may be reacted with a' chain-extending agent which is an organic compound containing a plurality of active hydrogen atoms capable of reacting with isocyanates, there being no more than two atoms in the chain-extending agent having active hydrogen attached thereto. Representative chainextending agents include compounds such as ethylene glycol, 2-allyloxymelhyl-2-methyl-1,3propanediol, hexamethylene glycol, diet hylene glycol, etc. 7

As mentioned above, the curable polyether polyurethane polymers are cured according to the presentinvention by employing dimethylolethyleneurea as a curing agent in the presence of quinolinium tetrachlorozincate as a catalyst. The quinoliniurn 'tetrachlorozincate may be prepared according to the procedure described in Chemical Abstracts 29 (1935), page 2109.

In carrying out the curing process, the uncured polyether polyurethane polymer is compounded with the dimethylolethyleneurea and quinolinium tetrachlorozincate, preferably on a mill. If desired during the milling procedure, other compounding ingredients can be used such as carbon black, silica, variousplasticizers, dyes, etc. In the instances where the uncured polyether polyurethane is a liquid the curing agent and catalyst may be incorporated therewith simply by mixing. In such cases the liquid dimethylether of dimethylolethyleneurea may be used.

The compounded curable polymer is then subjected to heating at a temperature'of from about 120 to 160 C. in order for the curing reactionto take place. Temperatures of from about 140 to 150 C. are preferred. Normallythe curing reaction is carried out in a pressure mold for a curing time of from about 30 minutes to about 3 hours.

The amount of dimethylolethyleneurea which is used as a curing or cross-linking agent may vary between about 3 to 15 percent by weight based on the weight of the uncured polymer. It is to be understood that the amount of curing agent may vary depending on the degree of cure desired as well as the physical properties desired in the final cured product. It has been determined that if .less than about 3% by weight of curing agent is used the tensile strength and compression set of the cured elastomer will be deficient whereas the use of more than about 15% of curing agent is unnecessary in order to get satisfactory cures.

from about 0.1 to 1.0 percent by weight based on the weight of the uncured polymer.

The mechanism of the curing reaction involves the reaction ofthe terminal hydroxyl groups of dimethylol- 'ethyleneurea with the hydrogen atoms on the urethane nitrogen linkages in the uncured polymer whereby two such urethane nitrogen atoms are linked together by'the dim'ethylolethyleneurea residue. The cured elastomers will-therefore, contain a plurality of units of the formula oo-o-o-N-n- HiC-N /C=O mo-{N i i "-o oo-o N -R- wherein OGO- and R have the significance de- "fi'ned above. 7 d I d H The cured elastomers of the present invention are "characterized by having excellent physical properties, particularlygood abrasion resistance and good compres- 'sio'n set. Inladdition it has been determined that elasto- 'rriers having "good abrasion resistance may be obtained "according to the'curing process of the'pi'esent invention without compounding the "elastomer with carbon black. As a result of this, light colored elastomers with excellent physical properties may be obtained. The cured e1astoniers have many varied uses in common with other poly- ,"urethane elastomers in that they may be used in the preparation of tires, tubes, belts, hoses and tubing, 'wire and cable jackets, gaskets and thelike.

The basic elastomeric properties of the elastomers may be varied bysuitable'comp'ounding. The amount and typeof compounding agent incorporated in the stock is "dependent upon the use for which the elastomer is intended. Included amongtsuch'of the more important useful compounding agents are carbon black, clay, silica, talc, "and plasticizers. f

I The following examples'will better illustfatethe'n'atiire of the present invention; however, the invention is not intended to be limited to these examples. Parts are by weight unless otherwise indicated.

The following methods were used to carry out the tests for evaluating elastomers:

Heat build-up: D623-52T (Method A) Compression set: D395-53T (Method B, 22 hrs 70 C.

and 70 hrs., 100C.)

Stress strain: Williams ring tester EXAMPLE 1 Parts by Weight Polymer .t 100 100 High abrasion furnace black 30 Silica filler- 30 Dimethylolethyleneurea 6 ,6 Quinolinium tetrachlorozincate 0. 35 0. 35

Samples of the compounded polymers were then cured at 150 C. for minutes. The following table indicates the physical properties of the cured elastomers:

Table I Modulus at 300% elongation, 25 C. (lb in?) 600 Tensile at break, 25 C. (lb in?) 2, 300 3. 200 Elongation at break, 25? C.7(percent) 220 700 Tensile at break, 70 0. (lb. in. 500 1, 300 Yerzley resilience, 25 0. (percent) 61 Compression set, 70 0. (percent) 23 Shore A hardne s 75 75 Abrasion test: N .B.S.Index 286 387 The elastomer compounded according to Formula B was white, since no furnace black was used, and it is obvious from the above that its abrasive properties are excellent.

EXAMPLE 2 A polyalkylene'ether polyurethane polymer is prepared by adding 3 moles of 2,4-toluenediisocyanate to one mole 'of 3-,(allyloxy)-1,2-propanediol and the mixture'thus obtained is agitated for 3 hours at 80 C. under an atmosphere of nitrogen. Then 2 moles of, apolytetramethyleneetherglycol of molecular weight 1000 is added and the mass'is agitated at 80 or one hour. Finally, it is transferred to ,a polyethylcnelined container and heated in an oven at'80 for 72 hours. A rubbery polymer is obtained.

This polymer is compounded on a rubber roll mill employing the usual procedure. A number of formulations are compounded, each one containing parts of the polymer, 30 parts of high abrasion furnace black, and varying amounts of dimethylolethyleneurca and quinolinium tetrachlorozincate. The following table illustrates the recipes used:

Table II a B o D V E F 100 100 100- v 100 100 100 h '30 3o 30 a0 a0 30 Qurnolmlum tetrachlorozincate. 0. 1 0:1 0. 5 0. 5' 0. 35 1.0 'Dimethylolethyleneurea 1 3 V 3 6.25 12.5 3

Samples of the above formulations were cured .at 150 C. for 80 minutes to yield elastomcrs having the properties set out in the following table: 1

As many widely difierent embodiments of this invention may be made Without departing from the spirit and scope thereof, it is to be understood that this invention is not limited to the specific embodiments thereof ex Table v5 cept as defined in the appended claims.

a What is claimed is: A B O D E F j 1. A cured polyurethane elastomer obtained by heatcuring a curable polyether polyurethane polymer with M i? bl/111") '5" 4 N,N'-dimethylolethyleneurea, said polyurethane polymer 3, .(1b./1n. 2,300 3,500 5,000 3,500 2,.00 4,100 E 25: 3. (percent) 620 370 22 180 450 being substantially free of uncombined isocyanate radiggf g (1) L250 2,000 L300 900 cals and consisting essentially of a plurality of units of y resihence at 0. (percent) 57 e2 63 0a 69 59 the formula 100 0. (percent)-- 58 71 74 86 86 69 Compression set, 70 C. 0 0 (percent) 70 30 1s 10 27 H H Shore A hardness 69 71 72 71 I8 72 15 1 Too soft to measure. wherein OG--O is a bivalent radical obtained by XAMPLE 3 removing the terminal hydrogen atoms from a polyether H I h 1 h Ad b glycol having a molecular weight of from about 750 to g g fi i g gg fi ig igg gg giggi g gi 33: 20 about 5,000, said glycol being selected from the group ing a molecular weight of 1000 with 4 moles of 24- conslsmig of polyalkyleneether ,glycols polyalkylelw C f 4 h Th ether-tlnoether glycols and polyalkylene-aryleneether glytolu.enednsocyanate at 8 and ours C cols, and R is a bivalent organic radical which is inert sulting product was capped by adding 2 moles of allyl to isocyanate groups alcohol agltatmg thoroughly 2. A cured elastomer according to claim 1 wherein the The hqmd Product was compounded as follows bivalent radical OGO- is obtained by removing Polymer 40 the terminal hydrogen atoms from a polytetramethylene- Dimethylolethyleneurea 4.9 ether glycol. Quinolinium tetrachlorozincate 0.14 3. A cured elastomer according to claim 2 wherein After heating the compounded elastomer at 140 C. for R i i radical 0 d 1 hi h about 5 minutes, a tough rubbery gel was obtained which process. or Preparm a Cure 6 asmmer w c had very good resilience comprises heatmg a polyether polyurethane polymer to a temperature of from about 120 to 160 C. with from EXAMPLE 4 b about 3 to 15 percent by weight of the polymer of A number of formulations we e mad using the poly- N,N-dimethylolethyleneurea in the presence of from 0.1 mer prepared of Example 2: to 1.0 percent by weight of the polymer of quinolinium Table IV A B c D E F G Polymer of Ex. 2 100 110 100 100 100 100 100 High abrasion furnace blank 30 30 30 30 Carbon black-.- 30 Colloidal silica filler 30 Clay filler 30 Quinolinium tetrachlorm 0.35 0.45. 0.55 0.35 0.35 0.35 0.35 Dimethylolethyleneurea 6 8 9 6 6 6 6 V Dioctylphfhalatn 15 Hydroxyl terminated polytetramethylene ether methane plasticizen- 15 3O On curing at 150 C. for 80 minutes, the compounded tetrachlorozincate, said polyurethane polymer being subpolymers had the following physical properties: stantially free of uncombined isocyanate radicals and consisting essentially of a plurality of units of the for Table V 5 mula A B 0 D E F G H I -o-G-0-o-NH R-Nn-o- M 25 0. (1b.! 33 0 0 5 mm 2,700- 1,700 3,500 2:283 3:555 wherein -OG O- is a bivalent radical obtained by 133,25 0. (perremoving the terminal hydrogen atoms from a polyether g gl'5 '5 5 333 388 :58 56:; 333 3 glycol having a molecular weight of from about 750 to Yerz leoy resilience, about 5,000, said glycol being selected from the group ggg gg? 66 59 73 68 75 consisting of polyalkyleneether glyeols, polyalkylene- ()percent) a 65 ether-thioether glycols and polyalkylene-aryleneether glyff g 'g gf' 20 26 23 22 cols, and R is a bivalent organic radical which is inert 1901 (percent) 8 5 55 to isocyanate groups. fgi flawless" "55' 7O 66 65 3 g 66 5. A process according to claim 4 wherein the poly- Heag blggd ypi ether polyurethane polymer is prepared from a polytetra- Fi 1, 2 inflsL 10 u 33 6 20 Q 3 70 lrnetiiygfeiseethgrzgtlycbl havifig a molecular weight of at ma. cen er eas an -to uene socyanate. fi5 163 166 171 148 158 196 159 6. A process according to claim 4 wherein the polymdeX 351 471 431 338 286 257 132 ether polyurethane polymer is prepared by reacting 3- v (allyloxy)-1,2-propanediol with a molar excess of 2,4- 3TE- A=Fma1cmpressln mmimum mmpresswntoluene diisocyanate and reacting the resulting product m b. pm ieua ietu l'eiieemer lycol having 'aiiidle'cu'lar weight of at least 750. 7

Re fern'c'e's Cited in the 111601 this ptent UNITED STATES PATENTS Hoover t a1. Apr. 10, 1945 8 V Kieider EH11. Mar. 12, 19 5 7 Fraser et 211. July 30, 1 957 Stilmar Nov. 26, 1957 Maxey Sept. 2, 1958 K6111 Jan. '19, 1960 Csendes Ian. 19, 1960 

1. A CURED POLYURETHANE ELASTOMER OBTAINED BY HEATCURING A CURABLE POLYETHER POLYURETHANE POLYMER WITH N,N''-DIMETHYLOLETHYLENEUREA, SAID POLYURETHANE POLYMER BEING SUBSTANTIALLY FREE OF UNCOMBINED ISOCYANATE RADICALS AND CONSISTIN ESSENTIALLY OF A PLURALITY OF UNITS OF THE FORMULA 